Monoazo dyestuffs



Patented Nov. 21, 1939 UNITED STATES.

PATENT oFFicE MoNoAzo' DYESTUFFS Richard Fleischhauer, Frankfort-0n-the-Main Fechenheim, Germany, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application January 21, 1938, Se-

rial No. 186,082. In Germany January 25,

4 Claims.

The present invention relates to monoazodyestufis which are capable of being converted into their metal complex compounds, More particularly it relates to monoazodyestuffs of the general formula:

SOaNa can be converted into a metal complex group,

acids of the general formula:

with N-acylamino-hydroxynaphthalene sulfonic HOaS- OH wherein one X stands for an acylamino group and the other X stands for hydrogen.

The N -acylamino-hydi'oxynaphthalene sulfonic acids employed as coupling components are obtainable by acylating the corresponding aminohydroxynaphthalene sulfonic acids according to the usual methods. These aminohydroxynaphthalene sulfonic acids may be prepared by a caustic alkali melt of l-aminonaphthalene-3.G-disulfonic acid. The mixture of l-amino-S-hydroxynaphthalene-B-sulfonic acid and l-amino-G-hydroxynaphthalene-3-sulfonic acidformed may be resolved by taking account of the different solubilities of their salts. One may also acylate the above mixture of the two isomeric acids and use the mixture of isomeric N-acyl derivatives thus obtained for the formation of the monoazodyestuffs.

The new dyestufis can also be prepared by treating with suitable acylating agents thecorrespondingaminoazodyestuiis derived from the above aminohydroxynaphthalene sulfonic acids.

When aftertreated with metalliaing agents, for instance when chromed according to one of the usual methods in substance or on the fiber, the new dyestuffs yield valuable dyeings of excellent fastness properties.

The properties of the new dyestuffs may be varied by a suitable selection of the acyl radicles. For instance in the case of aliphatic acyl radicles such as the acetyl, propionyl, methoxyacetyl, butyryl, I chloroacetyl, ethylsulfonyl and carbethoxy radicle generally dyestufis are obtained of particularly good levelling power, whereas with aromatic 'acyl radicles,'such as the benzoyl, toluenesulfonyl and phenoxyacetyl radicles and their nuclear substitution products or also with aliphatic acyl radicles containing more than 4 car,- bon atomadyestuifs are formed of particularly good fastness properties.

In order to further illustrate my invention the following examplesare given, the parts being by Weight and all temperatures in degrees centirade, but I Wish it, however, to be understood that my invention is not limited to the examples given nor to the exact conditions stated therein.

' Example 1 19.9 parts of 4.6-dinitro-2-aminophenol are diazotized in the usual manner and the diazo solution obtained is combined in the presence of an excess of sodium carbonate with an aqueous solution of 35 parts of '1-benzoylamino-6naphthol- 3-sulfonic acid. When the combination is complete, the. dyestuff formed. of the formula:

v The wool material which has been dyed in an acid bath, is brought at about 70 into an acid bath, then the necessary amount of potassium chromate is added and the dyeings are heated to boiling for about 30 minutes in this bath, whereby the chromium complex compound of the dyestuff is formed on the fiber.

The dyestuff may also be treated in substance with chromium salts, for instance by heating to boiling the aqueous solution of the dyestuff together with an excess of chromium fluoride or chromium formate. In this manner a dark powder is obtained, soluble in water and dyeing wool fast dark-grey to black shades.

The analogous dyestufir obtained by employing 1-acetylamino-3-naphthol-6-sulfonic acid as coupling component, in the above example, yields somewhat more bluish black shades when aftertreated on the fiber with chromium salts.

Example 2 18.9 parts of l-chloro-6-nitro-2-aminophenol are diazotized in the usual manner and the diazo solution obtained is allowed to run into an aqueous solution of 29 parts of l-acetylamino-Iinaphol-G-sulfonic acid containing an excess of sodium carbonate. When the combination is complete, the dyestufi formed of the formula:

is separated and dried. It is a dark powder, soluble in water with a reddish blue and in concentrated sulfuric acid with a red-violet color, and it dyes wool from an acid bath blue shades. When aftertreated with chromium salts, bluish grey dyeings of good fastness to fulling, potting and light are obtained.

Similar dyestuffs, which yield on wool valuable bluish grey shades of very good fastness to fulling and light when aftertreated with chromium salts, are obtained by employing as coupling component, in the above example, for instance, 1- carbomethoxyamino-3-naphthol-6-sulfonic acid, 1-carbethoxyamino3-naphthol-fi sulfonic acid, l-benzoylamino-S-naphthol-G-sulfonic acid, 1- methoxyacetylamino-3-naphthol-6-sulfonic acid and the like.

Example 3 OH OH C1 SOaNa is separated and dried. It is a brown powder, soluble in water and in concentrated sulfuric acid with a red color, and dyes Wool red shades. When aftertreated with chromium salts blueviolet dyeings of good fastness to potting and light are obtained. The dyestufi exhibits a good levelling power.

The chromium complex compound of the dyestufi may be prepared in substance, for example, by heating the dyestufi together with chromium formate to about 110 to 120. The product thus obtained dyes wool from an acid bath fast violet shades.

Example 4 22.4 parts of 4-chloro-2-aminophenol-6-sulfonic acid are diazotized in the usual manner and the diazo solution obtained is combined at about 20 with an aqueous solution of parts of l-benzoylamino-3-naphthol-6-sulfonic acid containing an excess of sodium carbonate.

The dyestufi formed of the formula:

on ()H Naoas O-N=N NHO o-C Example 5 The diazo solution obtained by diazotizing 13.7

parts of 2-aminobenzoic acid in the usual manner iscombined with an aqueous solution of 29 parts of 1-acetylamino-6-naphthol-3-sulfonic acid containing an excess of sodium carbonate. The dyestufi formed of the formula:

is separated and dried. It is a brick-red powder, soluble in water with an orange and in con centrated sulfuric acid with an orange-red color, and dyes Wool from an acid bath bright orange shades. When aftertreated with chromium salts red dyeings of good fastness to fulling and light are obtained.

The identical dyestufi may be prepared in the following manner. The diazo solution obtained by diazotizing 12.7 parts of 2-aminobenzoic acid in the usual manner is combined with an aqueous solution of 25 parts of l-amino-G-naphthol-S- sulfonic acid containing an excess of sodium carbonate. The aminoazodyestuif thus obtained which dyes Wool red-brown shades, is separated, dissolved in water and treated with an excess of acetic anhydride, until thered-brown color of the solution has been converted into a clear orange color. Then the sodium salt of the acetylated dyestuff isseparated and dried.

Example 6 28.4 parts of 1-amino-2-hydroxy-6-nitronaphthalenel-sulfonic acid are diazotized and the paste of the diazo compound obtained is introduced into an aqueous solution of 29 parts of 1-acetylamino-3-naphthol-6-sulfonic acid in the presence of an excess of calcium hydroxide. The mixture is stirred until the combination is complete. Then the sodium salt of the dyestuff formed of the formula:

on N=N Nn-o o-om OzN some OaNa Example 7 18.9 parts of 4-chloro-6-nitro-2-aminophenol are diazotized in the usual manner and the diazo solution obtained is allowed to run into an aqueous solution of 38 parts of l-phenoxyacetyb amino-6-naphthol-3-sulfonic acid containing an excess of sodium carbonate. The dyestuif thus obtained of the formula:

NH-OO-CHz-O-O ?H O QNON=N 01 S O sNa is separated and dried. It is a dark powder, soluble in sodium carbonate solution with a bluishviolet and in concentrated sulfuric acid with a. blue-red color, and dyes wool very fast blue-grey shades when aftertreated with chromium salts.

The analogous dyestufi prepared by employe ing -nitro-2-aminophenol as diazo component is a dark powder which is soluble in sodium carbonate solution with a blue and in concentrated sulfuric acid with a pink color and dyes wool very fast green-grey shades when aftertreated with chromium salts.

Example 8 22.4 parts of 4-chloro-2-aminophenol-6-sulfonic acid are diazotized in the usual manner and the diazo solution obtained iscombined at about'20'with an aqueous solution'containing,

an excess of sodium carbonateand 29 parts of a mixture of about 75% l-acetylamino fi-naphthol-S-sulfoni'c acid and about 25% 1-acetyl-- amino-3-naphthol-6-sulfonic acid. (This mixture is obtainable by acetylating the mixture of the two isomeric aminohydroxynaphthalene sulfonic acids which is formed when l-aminonaphthalene-3.6-disulfonic acid is subjected to an alkaline melt.) When the combinationis complete, the dyestuff formed which consists in a mixture of the two isomeric compounds of the following formulae:

SOaNB.

and

on on NaOsS +N'=N- Nfi-o o-om c1 SOaNa is separated and dried. It is a dark powder, soluble in water with a reddish blue and in concentrated sulfuric acid with'a violet-red color, and dyes wool red shades. ,When aftertreated with chromium salts very fast blue dyeings are obtained.

By variation of the diazoand coupling components various further dyestufis may be obtained. The following table shows some examples thereof, but it is to be understood, that the scope'of my invention is not limited to these examples.

Shade on wool D t o 1 3 iazo componen oup ing component, s uric aci Solution nftertreated Dlrect wlth Chl'OlIllUJJl salts 2-aminobenzoic acid (a) l-acetylamino-3-naphtho1-6-sulfonic acid Dark-red.

o (b) 1-acetylamino-fi-naphthol-S-sulionic acid Red. G-nitro-Z-aminobenzoic acid (a) Dark-red.

o 5b) I Yellowish'red. Do. 5mitro-2-aminophenol c) 1-benzoylamino-3-naphthol-6-sulfonie acid Violet Greenish-grey.

Do (d) l-bBnzoylamino-fi-naphthol-Zi-sulfonic acid Bluish-red... Pm]; Bluish grey. 4-ch1oro-6-nitro-2-ammopheno1 (d) .do Blush-violet... Grey. 4-methyI-6-nitro-2-aminophenol (a) Reddish-violet. Brown Violettish-grey.

Do Bluish-red... Dark-red Grcyish-violet.

Do Reddish-v1o1et. Reddish-brown Bluish-grey. 4-nitro-6-methyl-2-aminophennl Bluisn-red Brown Blackish-brown.

o ed Dark-brown Dark-brown. 2-aminophenol-4-sulfonic acid (a Bluish-red. Red... Violet.

0. Red do Reddish-vio1et.- 4-nitro-6-ch1oro-2-aminonhpnnl (c) Bluish-red. Brownish-violet. Dark-brown. 4-methyl-5-nitro-2-aminophenol (d) Violettish-fed. Bluish-red Bluish-grey. 4-nitro-2-aminophcnol-6snlfonic acid (41).- Bluish-mi Dark-violet. Dark-brown.

4 chloro 2 aminophenol 6 sul- (a) Reddish vio- Orange-red Blue.

tonic acid. let.

D (b) Bluish-red. Brick-red Do. Do ((1)., ..do Brownish-red... Do. 4 methyl 2 aminophenol 6 sul- (a). Reddish vio- Red Do.

fonic acid. let.

D (bl Bluish-red Violettish-biue. Do (c) Redtdish vio- Blue.

e Do (11) Bluish-red. Violettish-blue.

' Shade on wool Color of the Diazo component Coupling component sulfuric acid solution Aftertreated 5 Direct with chromium salts 6-chloro-2-aminophenol Cherry-red- Reddish-brown. Violet.

Do Red "do Reddish-violet. -i-chloro-2-aminophenol (b) Reddish-violet B1uish-red Violet. 6-nitro-l-amino-2-hydroxynaphtha- 1-(4-methyl-bonzeue-sulfamido)-3-napl1tl1ol-6- Violet Darl:-vi0let Dark-grey.

10 lene-4-sulfonic acid. sulfonic acid.

Do l-(4-methyl-benzcne-sulfamido)-6-naphthoi-3- d0 do Do.

- sulfonic acid.

2-aminophenol-4-sulfonic acid di- (a) Bluish-red. Brick-red Violet.

ethylamide.

D0 (b) Red Red Reddish-violct.

Do 1 (c)... B1uisl1-red. Dull-red. Greyish-violet.

Do (d) Red" do Dark-violet.

-1-chloro-5-nitro-2-aminophenol (d) V o1ettisl1-red Bluish-grey.

'Do (c) Violet Greenisli-grey.

I claim: 3. The mixture of the two isomeric monoazo- 1. The monoazodyestufis of the formula: dyestuffs of the formulae:

OH OH OH I NaO ;s N=N -NHO 0- HS AN=N X 1 OaNa S03N8 and 1 l OH OH wherein A stands for the radlcle of a diazo com- I ponent selected from the group consisting of the o s benzene and naphthalene series containing in v NHOC,CHa o-position to the nitrogen atom a group capable of being metallized, one X stands for an acyla- 5 mino group and. the other X stands for hydrogen, (J1 some wfhmh f dye fi i gg 3 2 which dyestuff mixture yields on Wool very fast 0 9 en aS nesSprper1e$W en Tea blue shades when aftertreated with chromium ed with chromium salts. sa1ts 2. The monoazodyestufi of the formula: 4. The monoazodyestuff of the formula:

which dyestuff dyes wool very fast bluish grey shades when aftertreated with chromium salts.

which dyestufi yields on Wool very fast blackish brown shades when aftertr ated with chromium salts.

RICHARD FLEISCI-II-IAUER. 

